Inert solution-processable molecular chromophores for organic electronic devices

ABSTRACT

Small organic molecule chromophores containing a benzo[c][1,2,5]thiadiazole with an electron-withdrawing substituent W in the 5-position (5BTH), benzo[c][1,2,5]oxadiazole with an electron-withdrawing substituent W in the 5-position (5BO), 2H-benzo[d][1,2,3]triazole (5BTR) with an electron-withdrawing substituent W in the 5-position (5BTR), 5-fluorobenzo[c][1,2,5]thiadiazole (FBTH), 5-fluorobenzo[c][1,2,5]oxadiazole (FBO), or 5-fluoro-2H-benzo[d][1,2,3]triazole (FBTR) core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority benefit of U.S. Provisional PatentApplication No. 61/615,176, filed Mar. 23, 2012. The entire contents ofthat application are hereby incorporated by reference herein.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with United States government support undergrant no. DE-SC0001009 awarded by the Center for Energy EfficientMaterials of the Department of Energy. The government has certain rightsin the invention.

BACKGROUND OF THE INVENTION

Small-molecule bulk-heterojunction (SM BHJ) solar cells have become acompetitive alternative to the exhaustively studied polymer organicphotovoltaics (OPV). Intense investigation into the design and utilityof conjugated polymers for light harvesting has provided great insightinto the design and implementation of organic semiconductors for OPVtechnology, to the point where power conversion efficiencies (PCEs) upto 8.4% have been achieved. However, polymer systems inherently sufferfrom batch-to-batch variations and limited options for purification ofthe polymeric materials. Small-molecule semiconductors avoid thedrawbacks inherent to polymeric semiconductors, as they are monodispersein nature and, due to having a higher solubility than polymeric analogs,can be purified and characterized using standard organic chemistryprotocols. Additionally, modifications to fine-tune properties can bemade to small molecules more readily and with fewer complications.Recently, it has been demonstrated that small molecule-based solar cellscan achieve efficiencies comparable to that of polymer-based solarcells. See Sun, Y. et al., Nat. Mater. 2011, 11, 44-48; Welch, G. C.;Bazan, G. C. J. Am. Chem. Soc. 2011, 133, 4632-4644; Welch, G. C. etal., J. of Mater. Chem. 2011, 21, 12700-12709; Henson, Z. B. et al., J.Am. Chem. Soc. 2012, 134 (8), 3766-3779; Zhang, Y. et al., Chem.Commun., 2011, 47, 11026-11028; Peng, Q. et al., Adv. Mater. 2011, 23,4554-4558; and Sharif, M. et al., Teterahedron Lett. 2010, 51,2810-2812.

A small molecule system with a central electron-rich core, flanked byrelatively electron-poor units, and terminated with a π-conjugatedend-cap has been previously described (Welch et al., J. MaterialsChemistry 21(34):12700-12709 (2011); U.S. Provisional Patent Appl. No.61/416,251; International Patent Appl. No. PCT/US2011/061963; thecontents of these publications are hereby incorporated by referenceherein in their entireties). The success of this system is in large partdue to the inclusion of pyridal[2,1,3]thiadiazole (PT) as an acceptorunit. The PT-based compounds have led to fabrication of a SM BHJ solarcell with a PCE of 6.7% (see Sun et al., Nature Materials, 11:44-48(2011).

One drawback to using PT-based materials in fabrication of smallmolecule solar cells is that the cells must employ molybdenum oxide as ahole-transport layer (HTL) for maximum efficiency. Molybdenum oxide isthermally evaporated onto devices, which prevents the use of inexpensivesolution deposition during roll-to-roll manufacture. It would bepreferable to use a solution-processable HTL material, such aspoly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), orother doped conjugated polymers. However, PEDOT:PSS bears acidicprotons, which, when deposited at an interface with the active layer,will protonate the pyridyl nitrogen of the pyridal[2,1,3]thiadiazole.This protonation results in a drastic reduction in the PCE of devicesfabricated using PEDOT:PSS as the anode interlayer that use PTcontaining small molecule donors. Other systems with labile protons andprotonatable semiconductors will also lead to deterioration of powerconversion efficiency.

Thus, there is a need for high-efficiency small molecule materials whichdo not limit manufacturing options, and which do not have sites thatreact with materials such as PEDOT:PSS, other acidic materials, ormaterials deposited from an acidic solution. The present invention seeksto address the need for improved light harvesting molecules formolecular heterojunction devices by providing novel and advantageousmaterials for use in such devices.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to organicnon-polymeric chromophores containing the benzo[c][1,2,5]thiadiazolewith an electron-withdrawing substituent W in the 5-position (5BTH), ofthe following structure:

the benzo[c][1,2,5]oxadiazole with an electron-withdrawing substituent Win the 5-position (5BO), of the following structure:

or the 2H-benzo[d][1,2,3]triazole with an electron-withdrawingsubstituent W in the 5-position (5BTR) (and N2-substituted derivativesthereof) of the following structure:

where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

and where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F;

for use in heterojunction devices, such as organic small molecule solarcells and transistors. The organic non-polymeric chromophores can beused in an electronic or optoelectronic device, for example, in theactive layer of such a device.

In one embodiment, W is F. In one embodiment, W is C₁. In oneembodiment, W is Br. In one embodiment, W is I. In one embodiment, W is—CN. In one embodiment, W is —CF₃. In one embodiment, W is —CHF₂. In oneembodiment, W is —CH₂F.

In one embodiment, the present invention is directed to organicnon-polymeric chromophores containing the5-fluorobenzo[c][1,2,5]thiadiazole (FBTH) structure:

the 5-fluorobenzo[c][1,2,5]oxadiazole (FBO) structure:

or the 5-fluoro-2H-benzo[d][1,2,3]triazole (FBTR) structure (andN2-substituted derivatives thereof):

where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

for use in heterojunction devices, such as organic small molecule solarcells and transistors.

In one embodiment, the present invention is directed to non-polymericelectron-donating and electron-accepting chromophores having a corestructure of benzo[c][1,2,5]thiadiazole with an electron-withdrawingsubstituent W in the 5-position (5BTH), benzo[c][1,2,5]oxadiazole withan electron-withdrawing substituent W in the 5-position (5BO), or2H-benzo[d][1,2,3]triazole (5BTR) with an electron-withdrawingsubstituent W in the 5-position (5BTR). In another embodiment, thepresent invention is directed to non-polymeric electron-donating andelectron-accepting chromophores having a core structure of5-fluorobenzo[c][1,2,5]thiadiazole (FBTH),5-fluorobenzo[c][1,2,5]oxadiazole (FBO), or5-fluoro-2H-benzo[d][1,2,3]triazole (FBTR) core structure. In anotherembodiment, the present invention is directed to optoelectronic devicescomprising an active layer composition of a mixture of a non-polymericlight-harvesting electron-donating chromophore based on a 5BTH, 5BO,5BTR, FBTH, FBO, or FBTR core structure with an electron-acceptingmaterial, such as a fullerene, methanofullerene, rylene diimides orrelated π-conjugated organic electron acceptors. Organic or inorganicelectron acceptors can be used. In another embodiment, the presentinvention is directed to optoelectronic devices comprising an activelayer composition of a mixture of a non-polymeric light-harvestingelectron-accepting chromophore based on a 5BTH, 5BO, 5BTR, FBTH, FBO, orFBTR core structure with an electron-donating material. Organic orinorganic electron donors can be used. The present invention is alsodirected to methods of fabricating the devices by solution processing.In one embodiment, all active layers of the described optoelectronicdevices are formed from solutions comprising of non-polymeric discreteorganic materials.

In one embodiment, the invention embraces compounds of Formula I:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

and, in additional embodiments, compounds of Formula Ia, Formula Ib, andFormula Ic, Formula Ia-F, Formula Ib-F, and Formula Ic-F:

where A₁ is independently selected from substituted or unsubstitutedaryl or heteroaryl groups, such as C₆-C₃₀ substituted or unsubstitutedaryl or heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

where each B₁ is independently selected from substituted orunsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

where each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆alkyl group, or a substituted or unsubstituted aryl or heteroaryl group,such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups,C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, andC₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups.

In another embodiment, the invention embraces compounds of Formula II:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F;

n is an integer between 0 and 5, inclusive;

A₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In some embodiments of Formula II, X₁ and X₂ are each —C(W)— and Y₁ andY₂ are each CH. In some embodiments of Formula II, X₁ and X₂ are each CHand Y₁ and Y₂ are each —C(W)—. In any of the foregoing embodiments, Wcan be F.

In some embodiments of Formula II, X₁ and X₂ are each —C(W)—, Y₁ and Y₂are each CH and each M is S. In some embodiments of Formula II, X₁ andX₂ are each CH, Y₁ and Y₂ are each —C(W)—, and each M is S. In any ofthe foregoing embodiments, W can be F.

In some embodiments of Formula II, X₁ and X₂ are each —C(W)—, Y₁ and Y₂are each CH and each M is O. In some embodiments of Formula II, X₁ andX₂ are each CH, Y₁ and Y₂ are each —C(W)—, and each M is O. In any ofthe foregoing embodiments, W can be F.

In preferred embodiments, B₂ is selected from the group consisting of anonentity, H, F, a C₁-C₁₆ alkyl group, thiophene, benzothiophene,benzofuran, and benzothiazole.

In further embodiments, B₂ is phenyl, substituted at the p-position withdiphenylamine (i.e., the B₂ moiety is triphenylamine)

In another embodiment, the invention embraces compounds of Formula II ofFormula IIa, Formula IIb, Formula IIc, Formula IIa-F, Formula IIb-F, orFormula IIc-F:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in furtherembodiments, W is F;

n is an integer between 0 and 5, inclusive;

A₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and eachB₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In some embodiments of Formula IIa, each M is S.

In some embodiments of Formula IIa, each M is O.

In some embodiments of Formula IIb, each M is S.

In some embodiments of Formula IIb, each M is O.

In some embodiments of Formula IIc, each M is S.

In some embodiments of Formula IIc, each M is O.

In some embodiments of Formula IIa-F, each M is S.

In some embodiments of Formula IIa-F, each M is O.

In some embodiments of Formula IIb-F, each M is S.

In some embodiments of Formula IIb-F, each M is O.

In some embodiments of Formula IIc-F, each M is S.

In some embodiments of Formula IIc-F, each M is O.

In some embodiments, the compounds of Formula II are selected fromcompounds of Formula IId:

where Q₁ is C or Si;

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—;

W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in furtherembodiments, W is F;

n is 0, 1, 2, or 3;

R₇ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, benzofuran-2-yl,benzothiophene-2-yl, and benzothiazole-2-yl; and

R₈ is selected from H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IId, Q₁ is C.

In one embodiment of Formula IId, Q₁ is Si.

In one embodiment of Formula IId, X₁ and X₂ are —C(W)— and Y₁ and Y₂ areCH; in a further embodiment, W is F.

In one embodiment of Formula IId, X₁ and X₂ are CH and Y₁ and Y₂ are—C(W)—; in a further embodiment, W is F.

In one embodiment of Formula IId, n is 2.

In one embodiment of Formula IId, R₇ is selected from H or C₁-C₁₆ alkyl.

In one embodiment of Formula IId, R₇ is selected from benzofuran-2-yl.

In one embodiment of Formula IId, R₇ is selected frombenzothiophene-2-yl.

In one embodiment of Formula IId, R₇ is selected frombenzothiazole-2-yl.

In one embodiment of Formula IId, R₈ is selected from H or C₁-C₁₆ alkyl.

In one embodiment of Formula IId, R₈ is selected from C₁-C₁₆ alkyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, and Y₁and Y₂ are CH; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, and Y₁ andY₂ are —C(W)—; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, and Y₁and Y₂ are CH; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, and Y₁ andY₂ are —C(W)—; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, and n is 1; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, and n is 1; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, and n is 1; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, and n is 1; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 1, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 1, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 1, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 1, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 1, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 1, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 1, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 1, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, and n is 2; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, and n is 2; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, and n is 2; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, and n is 2; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 2, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 2, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 2, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 2, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 2, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 2, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 2, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 2, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, and n is 3; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, and n is 3; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, and n is 3; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, and n is 3; in a further embodiment of this type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 3, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 3, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 3, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 3, and R₇ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 3, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 3, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 3, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 3, and R₈ is 2-ethyl-hexyl; in a further embodiment ofthis type, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 3, and R₈ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 3, and R₈ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are —C(W)—, Y₁ andY₂ are CH, n is 3, and R₈ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are —C(W)—, n is 3, and R₈ is n-hexyl; in a further embodiment of thistype, W is F.

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In some embodiments of Formula II, the compounds are of Formula IIe:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F;

n is 0, 1, 2, or 3;

R₇ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, benzofuran-2-yl,benzothiophene-2-yl, benzothiazole-2-yl,4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, 4,4-bis(C₁-C₁₆alkyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene-2-yl, and4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl; and

R₉ is selected from H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl. In a furtherembodiment of this type, W is F.

In one embodiment of Formula IIe, n is 0.

In one embodiment of Formula IIe, n is 1.

In one embodiment of Formula IIe, n is 2.

In one embodiment of Formula IIe, n is 3.

In one embodiment of Formula IIe, X₁ and X₂ are —C(W)— and Y₁ and Y₂ areCH; in a further embodiment of this type, W is F.

In one embodiment of Formula He, X₁ and X₂ are CH and Y₁ and Y₂ are—C(W)—; in a further embodiment of this type, W is F.

In one embodiment of Formula He, R₉ is —O—C₁-C₁₆ alkyl.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉).

In one embodiment of Formula He, R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene-2-yl.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl.

In one embodiment of Formula He, R₉ is —O—C₁-C₁₆ alkyl and n is 0.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and n is 0.

In one embodiment of Formula He, R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene-2-yl and nis 0.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl and nis 0.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene-2-yl, X₁ andX₂ are —C(W)—, and Y₁ and Y₂ are CH; in a further embodiment of thistype, W is F.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene-2-yl, X₁ andX₂ are CH, and Y₁ and Y₂ are —C(W)—; in a further embodiment of thistype, W is F.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene-2-yl, X₁ andX₂ are —C(W)—, Y₁ and Y₂ are CH, and n is 0; in a further embodiment ofthis type, W is F.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene-2-yl, X₁ andX₂ are CH, Y₁ and Y₂ are —C(W)—, and n is 0; in a further embodiment ofthis type, W is F.

In one embodiment of Formula He, R₇ is n-hexyl.

In one embodiment of Formula He, R₉ is —O—C₁-C₁₆ alkyl and n is 1.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and n is 1.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and R₇ isn-hexyl.

In one embodiment of Formula He, R₇ is n-hexyl and n is 1.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl and n is 1.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are —C(W)—, and Y₁ and Y₂ are CH; in a furtherembodiment of this type, W is F.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are CH, and Y₁ and Y₂ are —C(W)—; in a furtherembodiment of this type, W is F.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are —C(W)—, Y₁ and Y₂ are CH, and n is 1; in afurther embodiment of this type, W is F.

In one embodiment of Formula He, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are CH, Y₁ and Y₂ are —C(W)—, and n is 1; in afurther embodiment of this type, W is F.

In some embodiments, the compounds of Formula II embrace compounds ofFormula IIf:

where R₉ is H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl, and where W is selectedfrom F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F. In a further embodiment,W is F.

In one embodiment of Formula IIf, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉).

In one embodiment of Formula IIf, R₉ is —O—(CH₂)₅CH₃.

In another embodiment, the invention embraces compounds of Formula III:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (Formula III-F);

where H₁ is selected from A₁, -B₁-B₂, -A₁-B₁-B₂, or

n is an integer between 0 and 5, inclusive;

A₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ (when present) is independently selected from a nonentity, H, F,a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl orheteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In another embodiment, the invention embraces compounds of Formula IIIof Formula IIIa, Formula Mb, Formula IIIc, and Formula IIId:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (Formula IIIa-F, Formula IIIb-F, FormulaIIIc-F, or Formula IIId-F);

n is an integer between 0 and 5, inclusive;

A₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ to substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ (when present) is independently selected from a nonentity, H, F,a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl orheteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In another embodiment, the invention embraces compounds of Formula IV-V:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; andwhere, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from—C(W)— and CH, where when X₃ is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃is —C(W)—;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each E₁ is independently either absent, or selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of aryl and heteroarylgroups include, but are not limited to, thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole; and

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula IV-V, each M is S. In one embodiment ofFormula IV-V, each D₁ is the same moiety. In one embodiment of FormulaIV-V, each D₂ is the same moiety. In one embodiment of Formula IV-V,each D₁ is the same moiety, and each D₂ is the same moiety(independently of D₁). In one embodiment of Formula IV-V, each M is S,each D₁ is the same moiety, and each D₂ is the same moiety(independently of D₁).

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each —C(W)— andY₁, Y₂, and Y₃, are each CH. In some embodiments of Formula IV-V, X₁,X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each —C(W)—.

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each —C(W)— andY₁, Y₂, and Y₃, are each CH, and each M is S. In some embodiments ofFormula IV-V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each—C(W)—, and each M is S.

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each —C(W)— andY₁, Y₂, and Y₃, are each CH, and each M is O. In some embodiments ofFormula IV-V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each—C(W)—, and each M is O.

In another embodiment, the invention embraces compounds of Formula IV-Vof Formula IV:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; andwhere, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from—C(W)— and CH, where when X₃ is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃is —C(W)—;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole; and

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula IV, each M is S. In one embodiment ofFormula IV, each D₁ is the same moiety. In one embodiment of Formula IV,each D₂ is the same moiety. In one embodiment of Formula IV, each D₁ isthe same moiety, and each D₂ is the same moiety (independently of D₁).In one embodiment of Formula IV, each M is S, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁).

In some embodiments of Formula IV, X₁, X₂, and X₃ are each —C(W)— andY₁, Y₂, and Y₃, are each CH; in further embodiments of this type, W isF. In some embodiments of Formula IV, X₁, X₂, and X₃ are each CH and Y₁,Y₂, and Y₃ are each —C(W)—; in further embodiments of this type, W is F.

In some embodiments of Formula IV, X₁, X₂, and X₃ are each —C(W)— andY₁, Y₂, and Y₃, are each CH, and each M is S; in further embodiments ofthis type, W is F. In some embodiments of Formula IV, X₁, X₂, and X₃ areeach CH and Y₁, Y₂, and Y₃ are each —C(W)—, and each M is S; in furtherembodiments of this type, W is F.

In some embodiments of Formula IV, X₁, X₂, and X₃ are each —C(W)— andY₁, Y₂, and Y₃, are each CH, and each M is O; in further embodiments ofthis type, W is F. In some embodiments of Formula IV, X₁, X₂, and X₃ areeach CH and Y₁, Y₂, and Y₃ are each —C(W)—, and each M is O; in furtherembodiments of this type, W is F.

In another embodiment, the invention embraces compounds of Formula IV ofFormula IVa or Formula IVb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (Formula IVa-F or Formula IVb-F);

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole; and

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula IVa, each M is S. In one embodiment ofFormula IVa, each D₁ is the same moiety. In one embodiment of FormulaIVa, each D₂ is the same moiety. In one embodiment of Formula IVa, eachD₁ is the same moiety, and each D₂ is the same moiety (independently ofD₁). In one embodiment of Formula IVa, each M is S, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁). In any ofthe foregoing embodiments, W can be F.

In one embodiment of Formula IVa, each M is O. In one embodiment ofFormula IVa, each D₁ is the same moiety. In one embodiment of FormulaIVa, each D₂ is the same moiety. In one embodiment of Formula IVa, eachD₁ is the same moiety, and each D₂ is the same moiety (independently ofD₁). In one embodiment of Formula IVa, each M is O, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁). In any ofthe foregoing embodiments, W can be F.

In one embodiment of Formula IVb, each M is S. In one embodiment ofFormula IVb, each D₁ is the same moiety. In one embodiment of FormulaIVb, each D₂ is the same moiety. In one embodiment of Formula IVb, eachD₁ is the same moiety, and each D₂ is the same moiety (independently ofD₁). In one embodiment of Formula IVb, each M is S, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁). In any ofthe foregoing embodiments, W can be F.

In one embodiment of Formula IVb, each M is O. In one embodiment ofFormula IVb, each D₁ is the same moiety. In one embodiment of FormulaIVb, each D₂ is the same moiety. In one embodiment of Formula IVb, eachD₁ is the same moiety, and each D₂ is the same moiety (independently ofD₁). In one embodiment of Formula IVb, each M is O, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁). In any ofthe foregoing embodiments, W can be F.

In another embodiment, the invention embraces compounds of Formula IV-Vof Formula V:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; andwhere, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from—C(W)— and CH, where when X₃ is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃is —C(W)—;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ and E₁ is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of aryl and heteroarylgroups include, but are not limited to, thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula V, each M is S. In one embodiment ofFormula V, each D₁ is the same moiety. In one embodiment of Formula V,each D₂ is the same moiety. In one embodiment of Formula V, each D₁ isthe same moiety, and each D₂ is the same moiety (independently of D₁).In one embodiment of Formula V, each M is S, each D₁ is the same moiety,and each D₂ is the same moiety (independently of D₁). In any of theforegoing embodiments, W can be F.

In some embodiments of Formula V, X₁, X₂, and X₃ are each —C(W)— and Y₁,Y₂, and Y₃, are each CH. In some embodiments of Formula V, X₁, X₂, andX₃ are each CH and Y₁, Y₂, and Y₃ are each —C(W)—. In any of theforegoing embodiments, W can be F.

In some embodiments of Formula V, X₁, X₂, and X₃ are each —C(W)— and Y₁,Y₂, and Y₃, are each CH, and each M is S. In some embodiments of FormulaV, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each —C(W)—, andeach M is S. In any of the foregoing embodiments, W can be F.

In some embodiments of Formula V, X₁, X₂, and X₃ are each —C(W)— and Y₁,Y₂, and Y₃, are each CH, and each M is O. In some embodiments of FormulaV, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each —C(W)—, andeach M is O. In any of the foregoing embodiments, W can be F.

In another embodiment, the invention embraces compounds of Formula Va orFormula Vb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (Formula Va-F or Formula Vb-F);

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ and E₁ is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of aryl and heteroarylgroups include, but are not limited to, thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula Va, each M is S. In one embodiment ofFormula Va, each E₁ is the same moiety. In one embodiment of Formula Va,each D₁ is the same moiety. In one embodiment of Formula Va, each D₂ isthe same moiety. In one embodiment of Formula Va, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Va, each M is S, and each E₁ is the same moiety,each D₁ is the same moiety, and each D₂ is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other). In any of theforegoing embodiments, W can be F.

In one embodiment of Formula Va, each M is O. In one embodiment ofFormula Va, each E₁ is the same moiety. In one embodiment of Formula Va,each D₁ is the same moiety. In one embodiment of Formula Va, each D₂ isthe same moiety. In one embodiment of Formula Va, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Va, each M is O, and each E₁ is the same moiety,each D₁ is the same moiety, and each D₂ is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other). In any of theforegoing embodiments, W can be F.

In one embodiment of Formula Vb, each M is S. In one embodiment ofFormula Vb, each E₁ is the same moiety. In one embodiment of Formula Vb,each D₁ is the same moiety. In one embodiment of Formula Vb, each D₂ isthe same moiety. In one embodiment of Formula Vb, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Vb, each M is S, and each E₁ is the same moiety,each D₁ is the same moiety, and each D₂ is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other). In any of theforegoing embodiments, W can be F.

In one embodiment of Formula Vb, each M is O. In one embodiment ofFormula Vb, each E₁ is the same moiety. In one embodiment of Formula Vb,each D₁ is the same moiety. In one embodiment of Formula Vb, each D₂ isthe same moiety. In one embodiment of Formula Vb, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Vb, each M is O, and each E₁ is the same moiety,each D₁ is the same moiety, and each D₂ is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other). In any of theforegoing embodiments, W can be F.

In another embodiment, the invention embraces compounds of FormulaVI-VII:

where the moiety

is selected from

(2, 2′,7,7′-yl-9,9′-spirobi[fluorene]),

(3,3′,7,7′-yl-5,5′-spirobi[dibenzo[b,d]silole]),

(2,2′,6,6′-yl-4,4″-spirobi[cyclopenta[1,2-b:5,4-b]dithiophene]), and

(2,2′,6,6′-yl-4,4′-spirobi[silolo[3,2-b:4,5-b]dithiophene]);

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; andwhere, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from—C(W)— and CH, where when X₃ is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃is —C(W)—; and where, independently of X₁, Y₁, X₂, Y₂, X₃, and Y₃, X₄and Y₄ are selected from —C(W)— and CH, where when X₄ is —C(W)—, Y₄ isCH, and when X₄ is CH, Y₄ is —C(W)—;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VI-VII, each M is S. In other embodimentsof Formula VI-VII, each M is O.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each—C(W)— and Y₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments ofFormula VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄are each —C(W)—. In any of the foregoing embodiments, W can be F.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each—C(W)— and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In someembodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁,Y₂, Y₃, and Y₄ are each —C(W)—, and each M is S. In any of the foregoingembodiments, W can be F.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each—C(W)— and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In someembodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁,Y₂, Y₃, and Y₄ are each —C(W)—, and each M is O. In any of the foregoingembodiments, W can be F.

In some embodiments of Formula VI-VII, each F₁ is the same moiety. Insome embodiments of Formula VI-VII, each G₁ is the same moiety. In someembodiments of Formula VI-VII, each G₂ is the same moiety. In someembodiments of Formula VI-VII, each F₁ is the same moiety, each G₁ isthe same moiety, and each G₂ is the same moiety (where F₁, G₁, and G₂are chosen independently of each other). In some embodiments of FormulaVI-VII, each F₁ is the same moiety, each G₁ is the same moiety, and eachG₂ is the same moiety (where F₁, G₁, and G₂ are chosen independently ofeach other); and M is S. In some embodiments of Formula VI-VII, each F₁is the same moiety, each G₁ is the same moiety, and each G₂ is the samemoiety (where F₁, G₁, and G₂ are chosen independently of each other);and M is O.

In another embodiment, the invention embraces compounds of Formula VI:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; andwhere, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from—C(W)— and CH, where when X₃ is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃is —C(W)—; and where, independently of X₁, Y₁, X₂, Y₂, X₃, and Y₃, X₄and Y₄ are selected from —C(W)— and CH, where when X₄ is —C(W)—, Y₄ isCH, and when X₄ is CH, Y₄ is —C(W)—;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀ tosubstituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VI, each M is S. In other embodiments ofFormula VI, each M is O.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each —C(W)—and Y₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VI,X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each —C(W)—.In any of the foregoing embodiments, W can be F.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each —C(W)—and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodimentsof Formula VI, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ areeach —C(W)—, and each M is S. In any of the foregoing embodiments, W canbe F.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each —C(W)—and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodimentsof Formula VI, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ areeach —C(W)—, and each M is O. In any of the foregoing embodiments, W canbe F.

In some embodiments of Formula VI, each F₁ is the same. In someembodiments of Formula VI, each G₁ is the same. In some embodiments ofFormula VI, each G₂ is the same. In some embodiments of Formula VI, eachF₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁,G₁, and G₂ are chosen independently of each other). In some embodimentsof Formula VI, each F₁ is the same, each G₁ is the same, and each G₂ isthe same (where F₁, G₁, and G₂ are chosen independently of each other);and M is S. In some embodiments of Formula VI, each F₁ is the same, eachG₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosenindependently of each other); and M is O.

In another embodiment, the invention embraces compounds of Formula VI,such as compounds of Formula VIa or Formula VIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (fluorine) (Formula VIa-F or Formula VIb-F);

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl; each G₁ is independently selected from substitutedor unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substitutedor unsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of aryl or heteroarylgroups include, but are not limited to, thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VIa, each M is S. In other embodiments ofFormula VIa, each M is O. In some embodiments of Formula VIa, each F₁ isthe same. In some embodiments of Formula VIa, each G₁ is the same. Insome embodiments of Formula VIa, each G₂ is the same. In someembodiments of Formula VIa, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other). In some embodiments of Formula VIa, each F₁ is the same,each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ arechosen independently of each other); and M is S. In some embodiments ofFormula VIa, each F₁ is the same, each G₁ is the same (where F₁, G₁, andG₂ are chosen independently of each other), and each G₂ is the same; andM is O. In any of the foregoing embodiments, W can be F (fluorine).

In some embodiments of Formula VIb, each M is S. In other embodiments ofFormula VIb, each M is O. In some embodiments of Formula VIb, each F₁ isthe same. In some embodiments of Formula VIb, each G₁ is the same. Insome embodiments of Formula VIb, each G₂ is the same. In someembodiments of Formula VIb, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other). In some embodiments of Formula VIb, each F₁ is the same,each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ arechosen independently of each other); and M is S. In some embodiments ofFormula VIb, each F₁ is the same, each G₁ is the same (where F₁, G₁, andG₂ are chosen independently of each other), and each G₂ is the same; andM is O. In any of the foregoing embodiments, W can be F (fluorine).

In another embodiment, the invention embraces compounds of Formula VII:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; andwhere, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from—C(W)— and CH, where when X₃ is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃is —C(W)—; and where, independently of X₁, Y₁, X₂, Y₂, X₃, and Y₃, X₄and Y₄ are selected from —C(W)— and CH, where when X₄ is —C(W)—, Y₄ isCH, and when X₄ is CH, Y₄ is —C(W)—;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (fluorine);

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VII, each M is S. In other embodiments ofFormula VII, each M is O.

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each —C(W)—and Y₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VII,X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each —C(W)—.In any of the foregoing embodiments, W can be F (fluorine).

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each —C(W)—and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodimentsof Formula VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄are each —C(W)—, and each M is S. In any of the foregoing embodiments, Wcan be F (fluorine).

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each —C(W)—and Y₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodimentsof Formula VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄are each —C(W)—, and each M is O. In any of the foregoing embodiments, Wcan be F (fluorine).

In some embodiments of Formula VII, each F₁ is the same. In someembodiments of Formula VII, each G₁ is the same. In some embodiments ofFormula VII, each G₂ is the same. In some embodiments of Formula VII,each F₁ is the same, each G₁ is the same, and each G₂ is the same (whereF₁, G₁, and G₂ are chosen independently of each other). In someembodiments of Formula VII, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other); and M is S. In some embodiments of Formula VII, each F₁is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁,and G₂ are chosen independently of each other); and M is O.

In another embodiment, the invention embraces compounds of Formula VII,such as compounds of Formula VIIa or Formula VIIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (fluorine) (Formula VIIa-F or FormulaVIIb-F);

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl.

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole.

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VIIa, each M is S. In other embodimentsof Formula VIIa, each M is O. In some embodiments of Formula VIIa, eachF₁ is the same. In some embodiments of Formula VIIa, each G₁ is thesame. In some embodiments of Formula VIIa, each G₂ is the same. In someembodiments of Formula VIIa, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where G₁ and G₂ are chosen independently ofeach other). In some embodiments of Formula VIIa, each F₁ is the same,each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ arechosen independently of each other); and M is S. In some embodiments ofFormula VIIa, each F₁ is the same, each G₁ is the same (where F₁, G₁,and G₂ are chosen independently of each other), and each G₂ is the same;and M is O. In any of the foregoing embodiments, W can be F (fluorine).

In some embodiments of Formula VIIb, each M is S. In other embodimentsof Formula VIIb, each M is O. In some embodiments of Formula VIIb, eachF₁ is the same. In some embodiments of Formula VIIb, each G₁ is thesame. In some embodiments of Formula VIIb, each G₂ is the same. In someembodiments of Formula VIIb, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other). In some embodiments of Formula VIIb, each F₁ is thesame, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂are chosen independently of each other); and M is S. In some embodimentsof Formula VIIb, each F₁ is the same, each G₁ is the same, and each G₂is the same (where F₁, G₁, and G₂ are chosen independently of eachother); and M is O. In any of the foregoing embodiments, W can be F(fluorine).

In additional embodiments, the invention embraces compounds of Formula1-2-3-4-5:

where P₁ is selected from

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when J is CH; and X is S when J is N; R₄ is selectedfrom aryl or aryl substituted with alkyl, such as C₆-C₃₀ aryl optionallysubstituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionallysubstituted with one or more C₁-C₁₆ alkyl groups, and C₆-C₁₀ aryl groupsoptionally substituted with one or more C₁-C₁₆ alkyl groups, and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5;

In additional embodiments, the invention embraces compounds of Formula1, Formula 2, Formula 3, Formula 4, or Formula 5:

In the structures for Formula 1, Formula 2, Formula 3, Formula 4, andFormula 5 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (Formula 1-F, Formula 2-F, Formula 3-F,Formula 4-F, or Formula 5-F);

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when J is CH; and X is S when J is N;

R₄ is selected from aryl or aryl substituted with alkyl, such as C₆-C₃₀aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, andC₆-C₁₀ aryl groups optionally substituted with one or more C₁-C₁₆ alkylgroups, and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5. In any of theforegoing embodiments, W can be F.

In additional embodiments, the invention embraces compounds of Formula6-7-8:

where P₂ is selected from:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when J is CH; and X is S when J is N;

R₆ is selected from aryl, perfluoroaryl, or aryl substituted with alkyl,such as C₆-C₃₀ aryl optionally perfluorinated or optionally substitutedwith one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionallyperfluorinated or optionally substituted with one or more C₁-C₁₆ alkylgroups, and C₆-C₁₀ aryl groups optionally perfluorinated or optionallysubstituted with one or more C₁-C₁₆ alkyl groups; and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5. In any of theforegoing embodiments, W can be F.

In additional embodiments, the invention embraces compounds of Formula6, Formula 7, or Formula 8:

In the structures for Formula 6, Formula 7, and Formula 8 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F (Formula 6-F, Formula 7-F, or Formula 8-F);

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when J is CH; and X is S when J is N;

R₆ is selected from aryl, perfluoroaryl, or aryl substituted with alkyl,such as C₆-C₃₀ aryl optionally perfluorinated or optionally substitutedwith one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionallyperfluorinated or optionally substituted with one or more C₁-C₁₆ alkylgroups, and C₆-C₁₀ aryl groups optionally perfluorinated or optionallysubstituted with one or more C₁-C₁₆ alkyl groups; and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5. In any of theforegoing embodiments, W can be F.

In additional embodiments, the invention embraces compounds of Formula9-10:

where

is selected from

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

n is an integer from 1 to 5 inclusive, and m is an integer from 0 to 5inclusive; and

where DONOR is as defined below.

In one embodiment, n is 1. In another embodiment, n is 2. In anotherembodiment, n is 3. In another embodiment, n is 4. In anotherembodiment, n is 5. In another embodiment, m is 0. In anotherembodiment, m is 1. In another embodiment, m is 2. In anotherembodiment, m is 3. In another embodiment, m is 4. In anotherembodiment, m is 5. In any of the foregoing embodiments, W can be F.

In additional embodiments, the invention embraces compounds of Formula 9or Formula 10:

In the structures for Formula 9 and Formula 10 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; in afurther embodiment, W is F;

n is an integer from 1 to 5 inclusive, and m is an integer from 0 to 5inclusive. In another embodiment, n is 1. In another embodiment, n is 2.In another embodiment, n is 3. In another embodiment, n is 4. In anotherembodiment, n is 5. In another embodiment, m is 0. In anotherembodiment, m is 1. In another embodiment, m is 2. In anotherembodiment, m is 3. In another embodiment, m is 4. In anotherembodiment, m is 5; and

where DONOR is as defined below.

In the structures for Formula 1-2-3-4-5, Formula 1, Formula 2, Formula3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8,Formula 9-10, Formula 9, and Formula 10 above, each DONOR moiety isindependently selected from the following group:

where X is C or Si;

A is N or P;

R₁₁ is selected from C₁-C₁₆ alkyl;

R₁₂ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl,C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl;

R₁₃ is selected from C₁-C₁₆ alkyl or C₆-C₂₀ aryl;

R₁₄ is selected from C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, —C(═O)—O—C₁-C₁₆alkyl, or —O—C(═O)—C₁-C₁₆ alkyl; and

R₁₅ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl,C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl; and

R₁₆ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl,C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl.

The DONOR structures are depicted as divalent; when a DONOR subunit ismonovalent (as, for example, in Formula 9-10, Formula 9, and Formula 10above), one valence is attached to the structure as depicted in theFormula, and one valence is terminated with H or C₁-C₂₀ alkyl, such ashexyl or 2-ethylhexyl.

In further embodiments, in the structure for Formula 1-2-3-4-5, eachDONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 1, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 2, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 3, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 4, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 5, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 6-7-8, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 6, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 7, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 8, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 9-10, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 9, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 10, each DONORmoiety is the same moiety.

In any of the foregoing embodiments, W can be F.

In additional embodiments, the invention embraces electronic andoptoelectronic devices comprising a non-polymeric compound, saidcompound incorporating one or more groups of Formula A:

where said non-polymeric compound is an electron acceptor or is anelectron donor in an active layer of the electronic or optoelectronicdevice, where M is selected from sulfur (S), oxygen (O), or N—R₁, whereR₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl, and either X₁ is CH and Y₁ is—C(W)—, or X₁ is —C(W)— and Y₁ is CH. In one embodiment, where more thanone moiety of Formula A is present, M, X₁, and Y₁ for each moiety ischosen independently of the other moiety or moieties. In anotherembodiment, where more than one moiety of Formula A is present, M is thesame for each moiety, X₁ is the same for each moiety, and Y₁ is the samefor each moiety. In any of the foregoing embodiments, W can be F.

In additional embodiments, the invention embraces electronic andoptoelectronic devices comprising a non-polymeric compound, saidnon-polymeric compound comprising a benzo[c][1,2,5]thiadiazole with anelectron-withdrawing substituent W in the 5-position (5BTH), abenzo[c][1,2,5]oxadiazole with an electron-withdrawing substituent W inthe 5-position (5BO), a 2H-benzo[d][1,2,3]triazole with anelectron-withdrawing substituent W in the 5-position (5BTR),a5-fluorobenzo[c][1,2,5]thiadiazole (FBTH), a5-fluorobenzo[c][1,2,5]oxadiazole (FBO), or a5-fluoro-2H-benzo[d][1,2,3]triazole (FBTR) moiety, wherein saidnon-polymeric compound is an electron acceptor or is an electron donorin an active layer of the electronic or optoelectronic device.

In additional embodiments, the invention embraces electronic andoptoelectronic devices utilizing the compounds described above.

In additional embodiments, the invention embraces optoelectronicdevices, such as organic solar cells, with the general devicearchitecture using the compounds described above as a light harvestingelectron donor, comprising:

1) a first hole-collecting electrode, optionally coated onto atransparent substrate;

2) an optional layer or layers adjacent to the first electrode, such asan electron-blocking, exciton-blocking, or hole-transporting layer;

3) a layer comprising a mixture of an electron acceptor, such as anorganic electron acceptor or an inorganic electron acceptor, and anorganic non-polymeric electron donor, said donor comprising one or morecompounds selected from Formula I, Formula Ia, Formula Ib, Formula Ic,Formula II, Formula IIa, Formula IIb, Formula IIc, Formula III, FormulaMa, Formula Mb, Formula IIIc, Formula IIId, Formula IV-V, Formula IV,Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb, FormulaVI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII, Formula VIIa,Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3,Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8,Formula 9-10, Formula 9, or Formula 10;

4) an optional layer or layers such as hole-blocking, exciton-blocking,or electron-transporting layers; and

5) a second electron-collecting electrode.

In additional embodiments, the invention embraces optoelectronicdevices, such as organic solar cells, with the general devicearchitecture using the compounds described above as a light harvestingelectron acceptor, comprising:

1) a first hole-collecting electrode, optionally coated onto atransparent substrate; 2) an optional layer or layers adjacent to thefirst electrode, such as an electron-blocking, exciton-blocking, orhole-transporting layer;

3) a layer comprising a mixture of an electron donor, such as an organicelectron donor or an inorganic electron donor, and an organicnon-polymeric electron acceptor material selected from Formula I,Formula Ia, Formula Ib, Formula Ic, Formula II, Formula IIa, FormulaIIb, Formula IIc, Formula III, Formula IIIa, Formula Mb, Formula IIIc,Formula IIId, Formula IV-V, Formula IV, Formula IVa, Formula IVb,Formula V, Formula Va, Formula Vb, Formula VI-VII, Formula VI, FormulaVIa, Formula VIb, Formula VII, Formula VIIa, Formula VIIb, Formula1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5,Formula 6-7-8, Formula 6, Formula 7, Formula 8, Formula 9-10, Formula 9,or Formula 10;

4) an optional layer or layers such as hole-blocking, exciton-blocking,or electron-transporting layers; and

5) a second electron-collecting electrode.

In additional embodiments, the invention embraces devices such asorganic field-effect transistors with the general device architectureusing the compounds described above as a hole transporting medium,comprising:

1) a dielectric substrate; in one embodiment, this dielectric substrateis Si/SiO₂;

2) an optional layer or layers adjacent the dielectric substrate, usedto modify the surface energy of the dielectric and/or to facilitatedeposition of the active layer;

3) an active layer comprising an organic non-polymeric hole transportingmaterial selected from Formula I, Formula Ia, Formula Ib, Formula Ic,Formula II, Formula IIa, Formula IIb, Formula IIc, Formula III, FormulaMa, Formula Mb, Formula IIIc, Formula IIId, Formula IV-V, Formula IV,Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb, FormulaVI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII, Formula VIIa,Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3,Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8,Formula 9-10, Formula 9, or Formula 10; and

4) a metal electrode to facilitate charge injection and collection.

In additional embodiments, the invention embraces devices, such asorganic field-effect transistors with the general device architectureusing the compounds described above as an electron transporting medium,comprising:

1) a dielectric substrate; in one embodiment, this dielectric substrateis Si/SiO₂;

2) an optional layer or layers adjacent the dielectric substrate, usedto modify the surface energy of the dielectric and/or to facilitatedeposition of the active layer;

3) an active layer comprising an organic non-polymeric electrontransporting material selected from Formula I, Formula Ia, Formula Ib,Formula Ic, Formula II, Formula IIa, Formula IIb, Formula IIc, FormulaIII, Formula Ma, Formula Mb, Formula IIIc, Formula IIId, Formula IV-V,Formula IV, Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb,Formula VI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII,Formula VIIa, Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2,Formula 3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7,Formula 8, Formula 9-10, Formula 9, or Formula 10; and

4) a metal electrode to facilitate charge injection and collection.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the absorption spectra of (FIG. 1A) p-DTS(FBTTh₂)₂ solutionin chloroform, thin film and annealed film; (FIG. 1B) p-DTS(FBTTh₂)₂with various equivalents of trifluoroacetic acid in chloroform; and(FIG. 1C) d-DTS(PTTh₂)₂ with various equivalents of trifluoroacetic acidin chloroform.

FIG. 2 shows current voltage characteristics of solar cells with anactive layer comprised of p-DTS(FBTTh₂)₂ and PC₇₁BM as cast, annealedand with 0.4% (v/v) diiodooctane solvent additive.

FIG. 3 shows the external quantum efficiency of the solar cells of FIG.2.

DETAILED DESCRIPTION OF THE INVENTION Definitions

“Alkyl” is intended to embrace a saturated linear, branched, cyclic, ora combination of linear and/or branched and/or cyclic hydrocarbonchain(s) and/or ring(s) having the number of carbon atoms specified, orif no number is specified, having 1 to 16 carbon atoms.

“Alkenyl” is intended to embrace a linear, branched, cyclic, or acombination of linear and/or branched and/or cyclic hydrocarbon chain(s)and/or ring(s) having at least one carbon-carbon double bond, and havingthe number of carbon atoms specified, or if no number is specified,having 2 to 16 carbon atoms.

“Alkynyl” is intended to embrace a linear, branched, cyclic, or acombination of linear and/or branched and/or cyclic hydrocarbon chain(s)and/or ring(s) having at least one carbon-carbon triple bond, and havingthe number of carbon atoms specified, or if no number is specified,having 2 to 19 carbon atoms, preferably 2 to 16 carbon atoms.

“Fluoroalkyl” indicates an alkyl group where at least one hydrogen ofthe alkyl group has been replaced with a fluorine substituent.

“Aryl” is defined as an optionally substituted aromatic ring system.Aryl groups include monocyclic aromatic rings, polyaromatic ringsystems, and polycyclic aromatic ring systems containing the number ofcarbon atoms specified, or if no number is specified, containing six tothirty carbon atoms. In other embodiments, aryl groups may contain sixto twenty carbon atoms, six to twelve carbon atoms, or six to ten carbonatoms. In other embodiments, aryl groups can be unsubstituted.

“Heteroaryl” is defined as an optionally substituted aromatic ringsystem. Heteroaryl groups contain the number of carbon atoms specified,and one or more heteroatoms (such as one to six heteroatoms, or one tothree heteroatoms), where heteroatoms include, but are not limited to,oxygen, nitrogen, sulfur, and phosphorus. In other embodiments,heteroaryl groups may contain six to twenty carbon atoms and one to fourheteroatoms, six to twelve carbon atoms and one to three heteroatoms,six to ten carbon atoms and one to three heteroatoms, or three to sixcarbon atoms and one to three heteroatoms. In other embodiments,heteroaryl groups can be unsubstituted.

“Polymer” or “polymeric molecule” is defined herein as a structurecontaining at least eight repeating units. A “non-polymeric” molecule isa molecule containing seven or fewer repeating units. Thus, monomers,dimers, trimers, tetramers, pentamers, hexamers, and heptamers arenon-polymeric molecules for the purposes of this disclosure.Interruption of a repeating unit “resets” the count of subunits for thepurposes of this disclosure; thus, for example, for a molecule such asFormula 6:

when n is 5, the molecule is considered to have two separatefive-subunit pieces, that is, it is comprised of two pentathiopheneunits, and is not considered a decamer or 10-subunit polymer ofthiophene.

Non-polymeric molecules typically have a discrete molecular weight,while polymeric molecules typically have a distribution of molecularweights due to varying numbers of monomers that are incorporated intothe growing chain during polymerization. Thus, in one embodiment, apreparation of a non-polymeric molecule will be characterized by asingle molecular weight (where the molecular weight is averaged onlyover isotopic variation due to differing isotopes such as hydrogen,deuterium, carbon-12, carbon-13, etc.) of about 90%, preferably 95%,more preferably 98%, still more preferably 99%, of the molecularspecies. In contrast, preparations of a polymeric molecule willtypically have a distribution of molecular weights due to varyingnumbers of monomers in the final polymer, where the molecular weight isan average over each individual polymeric species present in a givenpreparation (measured in either number-average molecular weight orweight-average molecular weight).

Non-Reactive Electron Withdrawing Groups and Stabilization of ElectronicStructure

The current invention describes chromophores incorporatingbenzo[c][1,2,5]thiadiazoles with an electron-withdrawing substituent Win the 5-position (5BTH), benzo[c][1,2,5]oxadiazoles with anelectron-withdrawing substituent W in the 5-position (5BO),2H-benzo[d][1,2,3]triazoles (5BTR) with an electron-withdrawingsubstituent W in the 5-position (5BTR),5-fluorobenzo[c][1,2,5]thiadiazoles (FBTH),5-fluorobenzo[c][1,2,5]oxadiazoles (FBO), or5-fluoro-2H-benzo[d][1,2,3]triazoles (FBTR). One example of such amolecule is the solution-processed small-molecule donor:7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole),p-DTS(FBTTh₂)₂, where “p” refers to the fluorine atoms oriented proximalto the donor core; see Scheme 1 for an outline of the synthesis of thismolecule, and its structure.

The incorporation of a subunit of this type permits the manipulation ofelectronic levels without adding a reactive site, such as the pyridinenitrogen on pyridal[2,1,3]thiadiazole (PT)-type compounds, which issusceptible to protonation when deposited from acidic solution, or whenused with materials having labile protons such as PEDOT:PSS. In additionto being an excellent candidate as an acceptor unit, the fluorine atomalso imparts asymmetric reactivity to the corresponding dibromidecompound (such as FBTHBr₂), which allows for facile synthetic access tothe desired structure. Full synthetic details are provided in theExamples.

Optical properties were investigated using UV-visible absorptionspectroscopy. In both solution (chloroform) and solid state,p-DTS(FBTTh₂)₂ exhibits broad low energy transitions with favorableoverlap with the solar spectrum with λ_(max) values of 590 nm (solution)and 678 nm (solid state), and λ_(onset) values of 670 nm (solution) and800 nm (solid state), corresponding to optical band gaps of 1.85 and1.55 eV, respectively; see FIG. 1A. Thin film absorption exhibits ared-shifted spectrum as well as the development of vibronic structure inoptical profiles, typical of ordered thin films. Solution cyclicvoltammetry measurements indicated the highest occupied molecularorbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were −5.12and −3.34 eV, respectively, and line up appropriately with the frontiermolecular orbitals of common fullerene acceptors.

To probe acid sensitivity, the solution absorption profiles ofp-DTS(FBTTh₂)₂ (see Scheme 1, above) and d-DTS(PTTh₂)₂,

a pyridine-containing analog, were monitored as function ofconcentration of trifluoroacetic acid. FIG. 1B shows that the absorptionof p-DTS(FBTTh₂)₂ remains effectively unchanged with up to tenequivalents of acid. However, the pyridal analog shows significantchanges in its absorption spectrum as soon as acid is introduced, asshown in FIG. 1C. The effect manifests as a new low-energy transition,suggesting that the chromophore backbone, where low-energy transitiondipoles reside, is affected by the acid. These data indicatep-DTS(FBTTh₂)₂ is more resistant to acidity, and is suitable for usewith PEDOT:PSS interlayers without significant losses in performance.

Devices were fabricated with the general architecture ofITO/PEDOT:PSS/DTS(FBTTh₂)₂:PC₇₁BM/Ca/Al. Devices showed relatively poorperformance as cast, with a open circuit voltage (Voc) of 680 mV, shortcircuit current (Jsc) of 7.0 mA cm⁻², and a fill factor (FF) of 0.30,giving a power conversion efficiency (PCE) of 1.6%. Thermal annealing ofthe devices at 130° C. led to significant enhancement in Voc (820 mV),Jsc (11.0 mA cm⁻²), and FF (0.62), yielding a PCE of 5.6%. Processingwith a small amount (0.4% v/v) of diiodooctane (DIO) with a lowtemperature anneal (70° C.) led to a slightly lower Voc (809 mV), but asignificant increased current (12.8 mA cm⁻²) and fill factor (0.68)yielding a PCE of 7.0%; the highest reported efficiency of a solutionprocessed SM-BHJ solar cell known to the inventors as of filing. Thecurrent-voltage characteristics of the as-cast, thermally-annealed, and0.4% diiodooctane-low temperature annealed cells are shown in FIG. 2.The external quantum efficiency of the cells is shown in FIG. 3.

Other General Synthetic Procedures

The various molecules as illustrated herein are readily accessiblesynthetically by adaptation of the foregoing synthesis ofp-DTS(FBTTh₂)₂. For example, 5BTH moieties can be attached to abenzodithiophene core via the synthesis outlined in Scheme 2. Similarchemistry—that is, coupling of trimethylstannate derivatives of onemoiety to bromo derivatives of another moiety—can be employed toassemble any of the various molecules described herein.

Small Molecule Chromophores

The current invention provides several advantages for preparation ofoptoelectronic devices. The organic materials described arenon-polymeric allowing for synthesis and purification producers to bemore repeatable than organic polymers. Unlike polymers, the organicmaterials described are discrete mono-disperse small molecules whichallows for their exact structure to be known and reproduced. Synthesisof organic small molecule chromophores containing the 5BTH, 5BO, 5BTR,FBTH, FBO, or FBTR organic structures is straightforward, and methodsused for the pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine)organic structure (see M. Leclerc et al. Journal of the AmericanChemical Society, 2008, 130, 732) can be adapted to make the 5BTH, 5BO,5BTR, FBTH, FBO, and FBTR molecules (see also Welch et al., J. MaterialsChemistry 21(34):12700-12709 (2011); U.S. Provisional Patent Appl. No.61/416,251; and International Patent Appl. No. PCT/US2011/061963). Theasymmetry of the 5BTH, 5BO, 5BTR, FBTH, FBO, and FBTR structures allowsfor facile mono-functionalization of the PT structure. The organic smallmolecule chromophores described herein have relatively planar structuresallowing for good inter-chromophore interaction, which facilitatescharge transfer and transport.

The compounds are readily handled in solution, as the organic smallmolecule chromophores described retain good solubility in many commonorganic solvents, and are soluble in aqueous solvents, including acidicaqueous solvents. This allows solution processing during the preparationof the optoelectronic devices.

While solution processing is preferred for its ease of handling and lowcost, vapor deposition can also be used for the molecules, or mixturesof said molecules with other components, which are suitable for use insuch a method (e.g., vacuum deposition, physical vapor deposition,chemical vapor deposition).

Device Architectures, Materials, and Fabrication

In one embodiment, the optoelectronic device of the invention comprisesthe following layers:

a) a first hole-collecting electrode, optionally coated onto atransparent substrate;

b) an optional layer or layers adjacent to the first electrode, such asan electron-blocking, exciton-blocking, or hole-transporting layer;

c) a layer comprising a mixture of an electron donor of the generalFormula I-VII and an electron acceptor (donor:acceptor);

d) an optional layer or layers such as hole-blocking, exciton-blocking,or electron-transporting layers; and

e) a second electron-collecting electrode.

Typically, the first electrode can be transparent, allowing light toenter the device, but in some embodiments, the second electrode can betransparent. In some embodiments, both electrodes are transparent.

Typically, the first electrode (layer “a”) is deposited onto asubstrate, and the device is fabricated by subsequent deposition oflayers “b” (if present), “c”, “d” (if present), and “e”. However, thesecond electrode “e” can be deposited onto a substrate, with subsequentdeposition of layers “d” (if present), “c”, “b” (if present), and “a”.

In another embodiment, the optoelectronic device of the inventioncomprises the following layers:

a) indium tin oxide (ITO) coated onto a transparent substrate (a firstelectrode), where the transparent substrate can be glass, plastic, orany other transparent material compatible with ITO,

b) poly(3,4-ethylene dioxythiophene:poly(styrenesulfonate) (PEDOT:PSS)or a electron-blocking, exciton-blocking, or hole-transporting metaloxide, including, but not limited to, MoO3,

c) a mixture of electron-donating chromophores of the general FormulaI-VH, and an electron-acceptor (donor:acceptor), and

e) a metal electrode (a second electrode); where layer (d) in theprevious embodiment is absent.

Typically, the first electrode (layer “a”) is deposited onto thesubstrate, and the device is fabricated by subsequent deposition oflayers “b”, “c”, and “e”. However, the second electrode “e” can bedeposited onto a substrate, with subsequent deposition of layers “c”,“b”, and “a”.

The 5BTH, 5BO, 5BTR, FBTH, FBO, or FBTR electron donors or electronacceptors can be used in tandem solar cells, such as those disclosed inUS 2009/0126779. Tandem solar cells are arranged so that light which isnot absorbed by a first solar cell passes to a second solar cell, wherethe second solar cell typically has a smaller bandgap than the firstsolar cell in order to absorb electromagnetic radiation that cannot beusefully absorbed by the first solar cell. In an example of a tandemphotovoltaic device, the device can comprise a first cell and a secondcell arranged in tandem. The first cell is configured to receiveincident electromagnetic radiation and includes a first chargeseparating layer having a first semiconducting polymer adapted to createelectric charge carriers generated by electromagnetic radiation. Thesecond cell is configured to receive electromagnetic radiation passingout of the first cell in a light propagation path. The second cellincludes a second charge separating layer having a second semiconductingpolymer adapted to create electric charge carriers generated byelectromagnetic radiation. A layer separates the two cells, such as atitanium oxide layer which is interposed between the first and secondcells. The titanium oxide layer can be substantially amorphous and canhave a general formula of TiO_(x) where x is a number of about 1 toabout 1.96; that is, the titanium oxide layer can be sub-stoichiometrictitanium dioxide, or amorphous sub-stoichiometric titanium dioxide.

Passivating layers, such as those disclosed in US 2007/0221926 and US2007/0169816, can be incorporated into devices using the 5BTH, 5BO,5BTR, FBTH, FBO, or FBTR electron donors or electron acceptors.

Optical spacer layers, such as those disclosed in US 2006/0292736, canalso be employed in devices using the 5BTH, 5BO, 5BTR, FBTH, FBO, orFBTR electron donors or electron acceptors.

In one configuration, where light passes though a transparent firstelectrode (such as ITO-coated glass), it is absorbed by thedonor:acceptor mixture, which results in the separation of electricalcharges and migration of the charges to the electrodes, yielding ausable electrical potential.

The first electrode can be made of materials such as indium-tin oxide,indium-magnesium oxide, cadmium tin-oxide, tin oxide, aluminum- orindium-doped zinc oxide, gold, silver, nickel, palladium and platinum.Preferably the first electrode has a high work function (4.3 eV orhigher). Preferably, the first electrode is transparent.

The optional layer adjacent to the first electrode is preferablypolystyrenesulfonic acid-doped polyethylenedioxythiophene (PEDOT:PSS).Other hole transporting materials, such as polyaniline (with suitabledopants), orN,N′-diphenyl-N,N′-bis(3-methylphenyl)[1,1′-biphenyl]-4,4′-diamine(TPD), nickel oxide, can be used. Electron-blocking, exciton-blocking,or hole-transporting metal oxides, such as MoO₃, MoO_(3-x), V₂O_(5-x),NiO, Ta₂O₅, Ag₂O, CuO, Cu₂O, CrO_(3-x), and WO₃, where x is between 0.01and 0.99, more preferably between 0.1 and 0.9, can be used as materialsbetween the hole-transporting electrode and the active layer. Othersuitable materials are described in Greiner, Mark T. et al., “Universalenergy-level alignment of molecules on metal oxides,” Nature Materials,DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

One method of fabricating the optoelectronic device is as follows: Aconductive, transparent substrate is prepared from commerciallyavailable indium tin oxide-coated glass and polystyrenesulfonic aciddoped polyethylenedioxythiophene using standard procedures. A solutioncontaining a mixture of the donor and acceptor materials is prepared sothat the ratio of donor to acceptor is between 1:99 and 99:1 parts bymass; more preferably between 3:7 and 7:3 parts by mass. The overallconcentration of the solution may range between 0.1 mg/mL and 100 mg/mL,but is preferably in the range of 10 mg/mL and 30 mg/mL. In oneembodiment of the invention, 5BTH, 5BO, 5BTR, FBTH, FBO, or FBTRnon-polymeric molecules are used that have a solubility of at leastabout 0.1 mg/mL in an organic solvent, 1 mg/mL in an organic solvent, 5mg/mL, 10 mg/mL in an organic solvent, 30 mg/mL in an organic solvent,or 100 mg/mL in an organic solvent. The organic solvent can be selectedfrom chloroform, toluene, chlorobenzene, dichloromethane,tetrahydrofuran, or carbon disulfide.

The electron acceptor is preferably [6,6]-phenyl C61-butyric acid methylester (PCBM), but may be a different fullerene (including, but notlimited to, C71-PCBM), a tetracyanoquinodimethane, a vinazene, aperylene tetracarboxylic acid-dianhydride, a perylene tetracarboxylicacid-diimide, an oxadiazole, carbon nanotubes, or any other organicelectron acceptor, such as those compounds disclosed in U.S.2008/0315187.

In other embodiments, the electron acceptor is an inorganic acceptorselected from TiO₂ (titanium dioxide), TiO_(x) (titanium suboxide, wherex<2) and ZnO (zinc oxide). The titanium dioxide can be anatase, rutile,or amorphous. A titanium dioxide layer can be prepared by depositing asol-gel precursor solution, for example by spincasting or doctorblading,and sintering at a temperature between about 300° C. and 500° C. When aninorganic layer is used, component (c) of the optoelectronic devicedescribed above can be comprised of a layer of electron-donatingchromophores of the general Formula I-VII and an inorganicelectron-acceptor layer. Alternatively, the inorganic material can bedispersed in the electron-donating chromophores to create a singlelayer. Preparation of TiO₂ for use in solar cells is described in BrianO'Regan & Michael Grätzel, Nature 353:737 (1991) and Serap Günes et al.,2008 Nanotechnology 19 424009.

When titanium suboxide according to the formula TiO_(x) where x<2, isused, x is preferably 1<x<1.98, 1.1<x<1.9, 1.2<x<1.8, or 1.3<x<1.8. X inthe formula TiO_(x) can be <2, <1.98, <1.9, <1.8, <1.7, or <1.6.

Useful solvents include chloroform, toluene, chlorobenzene,dichloromethane, tetrahydrofuran, and carbon disulfide. However, thesolvent used may be any solvent which dissolves or partially dissolveboth donor and acceptor materials and has a non-zero vapor pressure.

The solution of donor and acceptor is deposited by spin casting,doctor-blading, ink-jet printing, roll-to-roll coating, slot-dyecoating, gravure coating, or any process which yields a continuous filmof the donor-acceptor mixture such that the thickness of the film iswithin the range of 10 to 1000 nm, more preferably between 50 and 150nm.

In certain embodiments, the layer of the donor and acceptor is cast froma solution comprising a solvent and the electron donor and the electronacceptor. The solvent can comprise chloroform, thiophene,trichloroethylene, chlorobenzene, carbon disulfide, a mixture of any ofthe foregoing solvents or any solvent or solvent mixture that dissolvesboth the donor and acceptor organic small molecule. The solvent can alsoinclude processing additives, such as those disclosed in US PatentApplication Publication Nos. 2009/0032808, 2008/0315187, or2009/0108255. For example, 1,8-diiodooctane (DIO) can be added to thesolvent/donor/acceptor mixture in an amount of 0.1-10% by volume. Theadditive, such as 2% DIO, can be added to any organic solvent used tocast the layer of donor/acceptor, such as chloroform. The solvent canalso include doping agents such as molybdenum trioxide (MoO₃). Forexample, MoO₃ can be added to the solvent/donor/acceptor mixture in anamount of 0.1-10% by volume.

An additional layer or layers of material (i.e., the layer(s) adjacentto the second electrode) may optionally be deposited on top of thedonor-acceptor film in order to block holes or excitons, act as anoptical buffer, or otherwise benefit the electrical characteristics ofthe device. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline can act as ahole-blocking or exciton-blocking material, while4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine andpolyethylene dioxythiophene can act as exciton-blocking materials. Othermaterials that can be used between the second electrode and the activelayer are titanium suboxide, ZnO, Cs₂CO₃, and ZrO₃. Additional materialssuitable for use are described in Greiner, Mark T. et al., “Universalenergy-level alignment of molecules on metal oxides,” Nature Materials,DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

Finally, an electrode, such as a metal electrode, is deposited on top ofthe structure by thermal evaporation, sputtering, printing, laminationor some other process. Conducting metal oxides, such as indium tinoxide, zinc oxide, or cadmium oxide, can also be used as electrodes, aswell as conducting organic materials, such as electrodes comprisinggraphene. For metal electrodes, the metal is preferably aluminum, silveror magnesium, but may be any metal. Nanowires such as silver nanowirescan also be used. If a transparent electrode is desired, very thinmetallic sheets of metals can also be used. In some embodiments, thedevice is annealed before and/or after evaporation of the metalelectrode.

Hole and electron mobilities are important parameters to consider in thefabrication/function of bulk heterojunction solar cells. For optimaldevice performance, a balance in the mobility of both charge carriers isdesirable. Preferably, the electron and hole mobilities are both on theorder of 10⁻⁴ cm²/Vs or higher. More preferably, the electron mobilitiesare on the order of 10⁻³ cm²/Vs or higher. In some embodiments, theelectron mobilities are on the order of 10⁻⁴ cm²/Vs or higher, and thehole mobilities are between 10⁻⁸ cm²/Vs and 10⁻⁴ cm²/Vs or higher. Inother embodiments, the electron mobilities are on the order of 10⁻³cm²/Vs or higher, and the hole mobilities are between 10′ cm²/Vs and10⁻⁴ cm²/Vs or higher.

Optoelectronic devices of the present invention have excellentphotovoltaic properties. In some embodiments, the power conversionefficiency (PCE) is at least 0.5%, at least 1.0%, at least 2.0%, or atleast 3.0%. In some embodiments, the short circuit current density isgreater than 3.0 mA/cm², and preferably greater than 8 mA/cm². In someembodiments, the open circuit voltage is between 0.3 and 1.0 V orhigher. In some embodiments, the device exhibits an external quantumefficiency of approximately 35% or greater between 300 and 800 nm.

The morphological properties of the donor:acceptor films can be measuredusing atomic force microscopy or other surface-sensitive techniques.Preferably, the films will have a root-mean-squared surface roughness ofless than 1.0 nm, more preferably less than 0.5 nm.

Inverted Device Architecture

In some cases, it can be advantageous to use inverted devicearchitecture, where the substrate act as a cathode, while the topelectrode acts as the anode. For example, using the substrate to collectelectrons can allow a stable, high work function metal such as gold ornickel to be used as the top electrode. This can be achieved bymodifying the work function of the substrate or using an n-typesubstrate. Inverted device architecture is described in, for example,Hau et al. (2010) “A Review on the Development of the Inverted PolymerSolar Cell Architecture,” Polymer Reviews 50(4):474-510, in Jen et al.,US 2009/0188558, and in Nguyen et al. US 2010/0326525 (see FIG. 19B).

In an example of a device using standard architecture, photo-generatedholes travel to an ITO substrate while photo-generated electrons travelto a top electrode consisting of a relatively low work-function metalsuch as Al. In a device using inverted architecture, the charge carriersflow in the opposite direction, where electrons travel to the ITOsubstrate while holes travel to the top electrode and are collected by arelatively high work function metal such as Au. This configuration hasthe advantage that a relatively stable metal is used as the topelectrode, which can increase the lifetime of the device.

For embodiments of the devices using an inverted device architecture,the first electrode can comprise Au or another material having a workfunction higher than the work function of the second electrode, whilethe second electrode can comprise an ITO substrate modified using aself-assembled monolayer of 3-aminopropyltrimethoxysiloxane or anothermaterial having a work function lower than the work function of thefirst electrode.

The compounds of the invention can also be used to make inverted tandemsolar cells, such as a cell having the layers of a transparentsubstrate, a transparent conductor, an electron injection/transportlayer, an active layer with a wider band gap organic semiconductor, ahole injection/transport layer, an electron injection/transport layer(which facilitates recombination between the front and back cells), anactive layer with a smaller band gap organic semiconductor, a holeinjection/transport layer, and a top metal electrode. An example of acell using this architecture is described in Dou et al., NaturePhotonics 6:180-185 (2012).

EXAMPLES General Experimental Procedures

Material Synthesis: Compound5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene{DTS(SnMe₃)₂} and 5′-Hexyl-2,2′-bithiophene-5-trimethylstannane wereprepared by methods similar to those reported in the literature (Coffin,R.; Peet, J.; Rogers, J.; Bazan, G. C. Nat. Chem. 2009; 1(8):657-661).Compound 5,5′-dibromo-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene(DTS-Bra) was purchased from Luminescence Technology Corp. (Lumtec) andused as received. Compound5′-Hexyl-2,2′,2″-trithiophene-5-trimethylstannane was prepared similarlyas in the literature (Leroy, J., Boucher, N., Sergeyev, S., Sferrazza,M. and Geerts, Y. H. Eur. J. Org. Chem. 2007, 1256-1261). Stannanesreported that were not purchased were prepared according to literatureprocedure (Coffin, R.; Peet, J.; Rogers, J.; Bazan, G. C. Nat. Chem.2009; 1(8):657-661).

Preparations were carried out on a bench top or under an atmosphere ofdry, oxygen-free nitrogen employing both Schlenk line techniques and aVacuum Atmospheres inert atmosphere glove box. Deuterated chloroform(CDCl₃) was purchased from Cambridge Isotopes Laboratory and used asreceived. All reactants and reagents are commercially available and usedas received, unless otherwise noted.

Compound5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene{DTS(SnMe₃)₂} and 5′-Hexyl-2,2′-bithiophene-5-trimethylstannane wereprepared by methods similar to those reported in the literature (Coffin,R.; Peet, J.; Rogers, J.; Bazan, G. C. Nat. Chem. 2009; 1(8):657-661).Compound 5,5′-dibromo-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene(DTS-Br2) was purchased from Luminescence Technology Corp. (Lumtec) andused as received. Compound5′-Hexyl-2,2′,2″-trithiophene-5-trimethylstannane was prepared similarlyas in the literature (Leroy, J., Boucher, N., Sergeyev, S., Sferrazza,M. and Geerts, Y. H. Eur. J. Org. Chem. 2007, 1256-1261). Stannanesreported that were not purchased were prepared according to literatureprocedure (Coffin, R.; Peet, J.; Rogers, J.; Bazan, G. C. Nat. Chem.2009; 1(8):657-661).

NMR: ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy spectrawere recorded on a Varian VNMRS 600 MHz Spectromenter at 25° C. unlessotherwise noted. ¹H and ¹³C NMR spectra are referenced to SiMe₄ usingthe residual solvent peak impurity of the given solvent. Chemical shiftsare reported in ppm and coupling constants in Hz as absolute values. 2DNOE ¹H-¹H correlation experiments were completed on a Bruker Avance-500MHz spectrometer at 25° C. for assignment of fluorine regiochemistry.

UV-vis: UV-visible spectroscopy were recorded using either a BeckmanCoulter DU 800 series or Perkin Elmer Lambda 750 spectrophotometer atroom temperature unless otherwise noted. All solution UV-vis experimentswere run in CHCl₃. Films were prepared by spin-coating CHCl₃ orchlorobenzene solutions onto glass substrates. Films were annealeddirectly on a hot plate for 2 minutes.

CHN: Combustion analyses were performed by the MSI analytical lab at theUniversity of California, Santa Barbara.

Mass Spectroscopy: Full scan, low resolution FD mass spectroscopy wascarried out at the Department of Chemistry Spectroscopy Facility,University of Californa, Santa Barbara.

DSC: Differential scanning calorimetry (DSC) was determined using a TAInstruments DSC (Model Q-20) with about 5 mg samples at a rate of 10°C./min in the temperature range of 0 to 300° C., unless otherwisestated.

Electrochemistry: All electrochemical measurements were performed usingCHI instrument model 730B in a standard three-electrode, one compartmentconfiguration equipped with Ag/AgCl electrode, Pt wire and Glassy carbonelectrode (dia. 3 mm), as the pseudo reference, counter electrode andworking electrode respectively. Glassy carbon electrodes were polishedwith alumina. The cyclic voltammetry (CV) experiments were performed inanhydrous dichloromethane solution with ˜0.1 M tetrabutylammoniumhexafluorophosphate (TBAPF₆) as the supporting electrolyte at scan rate50 mV/s unless otherwise stated. All electrochemical solutions werepurged with dry Ar for 15 minutes to deoxygenate the system. Solution CVmeasurements were carried out with a small molecule concentration of −1mg/mL in CH₂C₁₂. Ferrocene was used as an internal standard. The HOMOand LUMO levels were obtained by correlating the onsets (E_(ox)^(Fc/Fc+), E_(rd) ^(Fc/Fc+)) to the normal hydrogen electrode (NHE),assuming HOMO of Fc/Fc⁺ to be 4.88 eV.

Solubility Measurements: The solubility in a given solvent wasdetermined as follows: A saturated solution (˜30 mg/mL) was stirredovernight at 49° C. and then allowed to stand still for 24 hours. Theslurry was then filtered through a 0.45 μm PVDF filter. The filtrate isassumed to be a saturated solution. A 30 μL aliquot was then diluted to3 mL with chloroform. The UV-vis absorption spectrum was acquired andthe concentration determined using a standard calibration curve. Thecalibration curve was prepared by measuring the absorbance of 5solutions in chloroform with known concentrations and plotting λ_(max)vs concentration, wherein a linear relationship was observed.

Calculations: All calculations were performed using the Gaussian 03program. Optimized gas-phase ground state structures were calculated atthe density functional theory (DFT) level, using the hybrid B3LYPexchange-correlation functional and the split-valence 6-31G(d,p) basisset, i.e., B3LYP/6-31G(d,p). Frequency calculations were carried out toensure that the geometries obtained corresponded to minima and notsaddle points (i.e. global minima). California NanoSystems Institute atUCSB is acknowledged for computational resources.

Device Fabrication: Devices were prepared on cleaned, UV/ozone treatedCorning 1737 glass patterened with 140 nm ITO. Active layers were spuncast to give 100 nm thicknesses (as determined using an Ambios XP-100stylus profilometer) from solutions of p-DTS(FBTTh₂)₂ and PC₇₁BM at aweight ratio of 60:40 in chlorobenzene with or without 0.2% diiodooctane by volume, at an overall concentration of 35 mg mL⁻¹. Solutionswere heated for several hours and residual solids filtered prior tocasting at 90° C. Films were allowed to dry for 30 mins then heated to70° C. for 10 mins under inert atmosphere to drive off residual solvent.Cathodes were deposited by sequential thermal evaporation of 5 nm Cafollowed by 100 nm Al. Device characteristics were measured underillumination by a simulated 100 mWcm⁻² AM1.5G light source using a 300 WXe arc lamp with an AM 1.5 global filter. Solar-simulator irradience wascalibrated using a standard silicon photovoltaic with a protective KG1filter calibrated by the National Renewable Energy Laboratory. Externalquantum efficienceis were determined using a 75 W Xe source,monochromator, optical chopper, lock-in amplifier, and a NationalInstitute of Standards and Technology-calibrated silicon photodiode wasused for power-density calibration. Mismatch factors of the integratedquantum efficiency for devices was calculated to be less than 6%.

Example 1 Synthesis of 5-fluorobenzo[c][1,2,5]thiadiazole

In a three-neck round-bottom flask, 4-fluoro-1,2-benzenediamine (5.5 g,43.6 mmol) was fully dissolved in chloroform (500 mL) and triethylamine(30 mL). Thionyl chloride (7 mL, 96.0 mmol) was added drop wise viasyringe. The solution stirred at 80° C. overnight. The reaction wasallowed to cool and 250 mL of deionized water was added. The reactionwas transferred to a separatory funnel and was washed several times withwater. The organic phase was collected and dried over magnesium sulfate.The solution was filtered, concentrated and used directly. Recoveredyield: 4.75 g (70%). ¹H NMR (CDCl₃): δ 6.55 (dd, 1H, J=8.4, 5.4 Hz, CH),6.36 (dd, 1H, J=10.2, 3.0 Hz, CH), 6.31 (td, 1H, J=8.4, 3.0 Hz, CH).

Example 2 Synthesis of 4,7-dibromo-5-fluorobenzo[c][1,2,5]thiadiazole

A round-bottom flask was charged with 5-fluorobenzo[c][1,2,5]thiadiazole(2.23 g, 14.5 mmol) followed by 48% hydrobromic acid (30 mL). Molecularbromine (7.47 mL, 145 mmol) was added drop wise and the reactionrefluxed for 48 h. The reaction was allowed to cool to room temperatureand diluted with chloroform and deionized water. The bi-phasic mixturewas transferred to a separatory funnel and washed several times withwater, rinsed with saturated sodium sulfite and rinsed with saturatedsodium bicarbonate. Organics were collected and dried over magnesiumsulfate. The solution was filtered and concentrated with silica. Thecompound was purified by flash column chromatography using ahexanes/chloroform gradient. Isolation of pure fractions afforded awhite solid. Yield: 2.58 g (57%). ¹H NMR (CDCl₃): δ 7.79 (d, 1H, J=8.4Hz).

Example 3 Synthesis of 4-bromo-5-fluoro-7-(5‘-hexyl-[2,2’-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole

In a N2 filled glove box a 20 mL glass tube was charged with4,7-dibromo-5-fluorobenzo[c][1,2,5]thiadiazole (FBTBr2, 326 mg, 1.05mmol), 5′-Hexyl-2,2′-bithiophene-5-trimethylstannane (432 mg, 1.05mmol), Pd(PPh3)₄ (50 mg, 0.04 mmol) and Toluene (15 mL), and sealed witha Teflon® cap. The reaction mixture was heated to 80° C. for 48 h. Uponcooling, the material was then loaded onto silica and purified by flashchromatography using a hexanes/chloroform gradient. After fractioncollection and solvent removal an orange solid was obtained. Recoveredyield: 294 mg (64%). ¹H NMR (CDCl₃): δ 8.04 (d, J=3.6 Hz, 1H, CH), 7.67(d, J=10.2 Hz, 1H, CH), 7.19 (d, J=3.6 Hz, 1H, CH), 7.12 (d, J=3.6 Hz,1H, CH), 6.73 (d, J=3.6 Hz, 1H, CH), 2.82 (t, J=7.8 Hz, 2H, CH₂), 1.70(m, J=7.5 Hz, 2H, CH₂), 1.40 (br m, 2H, CH₂), 1.34 (br m, 2H, CH₂), 1.32(br m, 2H, CH₂), 0.90 (t, J=7.2 Hz, 3H, CH₃).

Example 4 Synthesis of7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b]dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole)

In a N2 filled glove box a 20 mL glass tube was charged with4-bromo-5-fluoro-7-(5′-hexyl-[2,2′-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole(325 mg, 0.675 mmol),5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene(250 mg, 0.338 mmol), Pd(PPh3)₄ (30 mg, 0.024 mmol) and Toluene (15 mL),and sealed with a Teflon® cap. The reaction mixture was heated to 100°C. for 1 minute, 125° C. for 1 minute, 140° C. for 10 minutes, 150° C.for 10 minutes, and 160° C. for 10 minutes using a Biotage microwavereactor. Upon cooling, the material was then loaded onto silica, washedwith methanol and purified by flash chromatography using ahexanes/chloroform gradient in duplicate. After fraction collection andsolvent removal a metallic purple solid was obtained. The solid wasslurried in a 3:1 mixture of methanol and hexanes, sonicated for 1 hourand stirred overnight. The suspension was filtered, washed with acetoneand dried in vacuo. The product was recovered as a metallic purplesolid. Recovered yield: 230 mg (56%). ¹H NMR (CDCl₃): δ 8.35 (t, 2H,CH), 8.05 (d, J=3.6 Hz, 2H, CH), 7.75 (d, J=6.9 Hz, 2H, CH), 7.20 (d,J=3.6 Hz, 2H, CH), 7.13 (d, J=3.6 Hz, 2H, CH), 6.74 (d, J=3.6 Hz, 2H,CH), 2.83 (t, J=7.5 Hz, 4H, CH₂), 1.71 (m, 4H, CH₂), 1.56 (br m, 2H,CH₂), {1.40 (br m, n₁H) −1.33 (br m, n₂H) −1.24 (br m, n₃H), wheren₁+n₂+n₃=30 H}, 1.14 (br m, 4H, CH₂), 0.91 (m, 6H, CH₃), 0.84 (br m,12H, CH₃).

The disclosures of all publications, patents, patent applications andpublished patent applications referred to herein by an identifyingcitation are hereby incorporated herein by reference in their entirety.

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity ofunderstanding, it is apparent to those skilled in the art that certainchanges and modifications will be practiced. Therefore, the descriptionand examples should not be construed as limiting the scope of theinvention.

1. An electronic or optoelectronic device comprising a non-polymericcompound, said compound incorporating one or more groups of Formula A:

where said non-polymeric compound is used in an active layer of theelectronic or optoelectronic device; where M is selected from sulfur(S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;where either X₁ is CH and Y₁ is —C(W)—, or X₁ is —C(W)— and Y₁ is CH;and W is selected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F.
 2. Theelectronic or optoelectronic device according to claim 1, wherein thenon-polymeric compound is used in an active layer of said device.
 3. Theelectronic or optoelectronic device according to claim 1, wherein saiddevice is a solar cell.
 4. The electronic or optoelectronic deviceaccording to claim 1, wherein M is sulfur and W is F.
 5. The electronicor optoelectronic device according to claim 1, wherein the active layercomprises a compound of Formula II:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; W isselected from F, Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; M is selectedfrom sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀ alkyl orC₆-C₃₀ aryl; n is an integer between 0 and 5, inclusive; A₁ isindependently selected from C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups; each B₁ is independently selected from C₆-C₃₀substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups; and each B₂ isindependently selected from a nonentity, H, F, a C₁-C₁₆ alkyl group, ora C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups.
 6. Theelectronic or optoelectronic device according to claim 5, wherein theactive layer comprises a compound of Formula IIa-F, Formula IIb-F, orFormula IIc-F:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where W is selected from F, Cl, Br, I, —CN,—CF₃, —CHF₂, or —CH₂F; where A₁ is independently selected from C₆-C₃₀substituted or unsubstituted aryl or heteroaryl groups; B₁ isindependently selected from a C₆-C₃₀ substituted or unsubstituted arylor heteroaryl group; each B₂ is independently selected from a nonentity,H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted or unsubstitutedaryl or heteroaryl group; and n is an integer between 0 and 5 inclusive.7. The electronic or optoelectronic device according to claim 6, whereinA₁ is independently selected from substituted or unsubstitutedthiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C₁-C₃₀alkyl or C₆-C₃₀ aryl.
 8. The electronic or optoelectronic deviceaccording to claim 6, wherein B₁ is independently selected fromsubstituted or unsubstituted thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.
 9. Theelectronic or optoelectronic device according to claim 1, wherein theactive layer comprises a compound of Formula I:

wherein X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where M isselected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H, C₁-C₃₀alkyl or C₆-C₃₀ aryl; where, independently of X₁ and Y₁, X₂ and Y₂ areselected from —C(W)— and CH, where when X₂ is —C(W)—, Y₂ is CH, and whenX₂ is CH, Y₂ is —C(W)—; where W is selected from F, Cl, Br, I, —CN,—CF₃, —CHF₂, or —CH₂F; A₁ is independently selected from C₆-C₃₀substituted or unsubstituted aryl or heteroaryl groups; each B₁ isindependently selected from substituted or unsubstituted aryl orheteroaryl groups; and each B₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl group.
 10. The electronic oroptoelectronic device according to claim 9, wherein A₁ is independentlyselected from substituted or unsubstituted thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene where R and R′=C₁-C₃₀ alkylor C₆-C₃₀ aryl.
 11. The electronic or optoelectronic device according toclaim 9, wherein each B₁ is selected from substituted or unsubstitutedthiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.
 12. Theelectronic or optoelectronic device according to claim 9, wherein thecompound of Formula I is selected from formulas Ia-F, Ib-F, or Ic-F:


13. The electronic or optoelectronic device according to claim 1,wherein the active layer comprises a compound of Formula III-F:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where H₁ is selected from A₁, —B₁-B₂,-A₁-B₁-B₂, or

n is an integer between 0 and 5, inclusive; A₁ (when present) isindependently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups; each B₁ (when present) is independently selected fromsubstituted or unsubstituted aryl or heteroaryl groups; and each B₂(when present) is independently selected from a nonentity, H, F, aC₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl or heteroarylgroup.
 14. The electronic or optoelectronic device according to claim13, wherein the compound of Formula III-F is selected from a compound ofFormula IIIa-F, Formula IIIb-F, Formula IIIc-F, or Formula IIId-F:


15. The electronic or optoelectronic device according to claim 1,wherein the active layer comprises a compound of Formula IV-V:

where X₁ and Y₁ are selected from —C(W)— and CH, where when X₁ is—C(W)—, Y₁ is CH, and when X₁ is CH, Y₁ is —C(W)—; and where,independently of X₁ and Y₁, X₂ and Y₂ are selected from —C(W)— and CH,where when X₂ is —C(W)—, Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; andwhere, independently of X₁, Y₁, X₂, and Y₂, X₃ and Y₃ are selected from—C(W)— and CH, where when X₃ is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃is —C(W)—; M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where W is selected from F, Cl, Br,I, —CN, —CF₃, —CHF₂, or —CH₂F; K₁ is independently selected fromsubstituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups; each E₁ isindependently either absent, or selected from substituted orunsubstituted aryl or heteroaryl groups; each D₁ is independentlyselected from substituted or unsubstituted aryl or heteroaryl groups;and each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆alkyl group, or a substituted or unsubstituted aryl or heteroaryl group.16. The electronic or optoelectronic device according to claim 15, wherethe compound of Formula IV-V is selected from a compound of FormulaIVa-F or Formula IVb-F:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where K₁ is independently selected fromC₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; each D₁is independently selected from C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups; and each D₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl group.
 17. The electronic oroptoelectronic device according to claim 15, where the compound ofFormula IV-V is selected from a compound of Formula Va-F or FormulaVb-F:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where K₁ is independently selected fromC₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; each D₁and E₁ is independently selected from C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups; and each D₂ is independentlyselected from a nonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀substituted or unsubstituted aryl or heteroaryl group.
 18. Theelectronic or optoelectronic device according to claim 1, wherein theactive layer comprises a compound of Formula VI-VII:

where the moiety

is selected from

(2, 2′,7,7′-yl-9,9′-spirobi[fluorene]),

(3,3′,7,7′-yl-5,5′-spirobi[dibenzo[b,d]silole]),

(2,2′,6,6′-yl-4,4″-spirobi[cyclopenta[1,2-b:5,4-b′]dithiophene]), or

(2,2′,6,6′-yl-4,4′-spirobi[silolo[3,2-b:4,5-b]dithiophene]); where X₁and Y₁ are selected from —C(W)— and CH, where when X₁ is —C(W)—, Y₁ isCH, and when X₁ is CH, Y₁ is —C(W)—; and where, independently of X₁ andY₁, X₂ and Y₂ are selected from —C(W)— and CH, where when X₂ is —C(W)—,Y₂ is CH, and when X₂ is CH, Y₂ is —C(W)—; and where, independently ofX₁, X₂, and Y₂, X₃ and Y₃ are selected from —C(W)— and CH, where when X₃is —C(W)—, Y₃ is CH, and when X₃ is CH, Y₃ is —C(W)—; and where,independently of X₁, X₂, Y₂, X₃, and Y₃, X₄ and Y₄ are selected from—C(W)— and CH, where when X₄ is —C(W)—, Y₄ is CH, and when X₄ is CH, Y₄is —C(W)—; where M is selected from sulfur (S), oxygen (O), or N—R₁,where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where W is selected from F,Cl, Br, I, —CN, —CF₃, —CHF₂, or —CH₂F; each F₁ is independently selectedfrom substituted or unsubstituted aryl or heteroaryl groups; each G₁ isindependently selected from substituted or unsubstituted aryl orheteroaryl groups; and each G₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstitutedaryl or heteroaryl group.
 19. The electronic or optoelectronic deviceaccording to claim 18, wherein the compound of Formula VI-VII isselected from a compound of Formula VIa-F or Formula VIb-F:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where each F₁ is independently selectedfrom C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; eachG₁ is independently selected from C₆-C₃₀ substituted or unsubstitutedaryl or heteroaryl groups; and each G₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl group.
 20. The electronic oroptoelectronic device according to claim 18, wherein the compound ofFormula VI-VII is selected from a compound of Formula VIIa-F or FormulaVIIb-F:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where each F₁ is independently selectedfrom C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups; eachG₁ is independently selected from C₆-C₃₀ substituted or unsubstitutedaryl or heteroaryl groups; and each G₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl group. 21-41. (canceled)